1-acyloxy-4, 7-methano-3a, 4, 7, 7a-tetrahydro-4, 5, 6, 7, 8, 8-hexachloroindenes and method of producing the same



Patented Nov. 7, 1850 i-ACYLOXY-L'l- METHANO -3a,4,'l,'la-TETRA- HYDRO-4.5.6133 HEXAOHLOROINDENES AND METHOD OF PRODUCING THE SAME Simon n. Herzfeld and Eugene r. Ordas, Chicago, Ill., asslgnors to Velsicol Corporation, Chicago. 111., a corporation of Illinois l No Drawing. Application July 22, 1948,

Serial No. 40,155 r 10 Claims. (Cl. 260-488) Thisiapplication is a continuation-in-part ofour c o-pending application. Serial No. 735,526,

illed March 18, 1947, now abandoned.

invention relates to the production of new and useful compositions of matter.

More specifically, this invention is concerned with, newv compositions of matter generally efined as acyloxy derivatives of theadduct oi hexachlorocyclopentadiene and cyclopentadiene, and to the method of production thereof.

.The Diels Alder reaction of hexahalocyclopentadienes with cyclopentadiene has been disclosed in the co -pending application of Hcrzfeld, Lidov and "Bluest one, Serial No. 581,172, iiled March 5, :1945,'and is symbolized as follows:

beuchlorocyciocyclopenta pentadien'e diene rue compo a with which this present invention. is concerned as the l-acyloxy-derivatives of chlordene, represented by the formula:

l-a'eylox'yiJ-methano-aaifl.h-tetrahydro-4,5,6,73,8- hexachloroidene The nature of It in the formula above will be more fully explained hereinafter.

, l-acyloxy-chlordene may be prepared from chlordene in accordance with the present invention by preparing the 1bromo-derivative of chlordane and subsequently replacing the-bromine atom of said derivative with an acyloxy group, all as more fully explained hereinafter.

The formation of l-bromo-chlordene is dependent upon the fact that in the resent of peroxides, bromine reacts with chlordene by substitution at the free methylene group. Small alnounst 0f peroxides are normally contained in the reactants, but to insure a suiiicient quantity it is preferable to add organic peroxides such as benz'oyl peroxide, lauryl peroxide, or ascaridol, in

the .ratio of about 0.001 to 0.01 mol peroxide per 1 mol of 'chlordene. A molior bromine. or preferably a slight excess thereof should be used per mol of chlordane; however, the ratio of these reactants can be'varied over a very wide range and any preference is based on economic rather than technical reasons. Bromination is accomplished by reacting liquid bromine, preferably contained in a relativelyinert solvent such as carbon tetrachloride, I chloroform, carbon disulfide, tetrachloroethylene, or the like, with chlordane contained in a solvent and in the resence of a peroxide "as aforesaid. ',For effective reaction, the bromine may be added to the chlordene in the manner illustrated in the subsequent example. The time required for the reaction to proceed to completion, that is, when either or both of the reactants are completely used up, will depend on the'concentration of reactant temperature, agitation and those other factors normally affecting reaction rates. It is not necessary that the reaction be completed,.or that such reaction be terminated at completion, but'large excesses of time should be avoided to minimize the formation of side' products. The time when the reaction starts. the approximate rate of reaction, and the time when the reaction is completed can be estimated by'ithe ratejand duration of time that hydrogen bromide is generated from the reaction mixture. The reaction will proceed to result in the formationofi-bromo chlordene over fairly broad ranges of temperature, such as, for example."between about'15-18 C. Reaction temperatures between about room temperature or slightly above to about 120 C. are very satisfactoryi and good yields of product can be obtained at a reasonably rapid rate at temperaturesoi' about 45 C. to 65 C. The reaction temperature can generally be adequately controlled by controlling the rate of introduction of bromine to the reaction mixture; however, external 'cooling or heating means can be utilized if desired. When the reaction is completed, or is otherwise abated after product is formed, the lbromo-chlordene .can be isolated by vacuum fractreating said bromo compound for from aboutv one-half to about twenty hours or longer, depending upon the nature and concentration "of reactants and the temperature employed, with the salt of an organic acid, such as the sodium, potassium or silver salt of organic carboxylic acids having up to about twenty carbon atoms per molecule including such acids as acetic, propionic, butyric, valeric, benzoic, acrylic, butenoic, pentenoic, teracry ic, cinnamic, lauric, elaidic. 'and similar type acids.

The reaction between the sodium salt of the acid above defined and l-bromo-chlordene is carried out in the presence of a relatively inert solvent preferably capable of dissolving the reactants substantially completely, such as ethylene glycol, carbitol, propionicacid, dioxane, glacial acetic acid or the free acid of the salt used 'as a. reactant. The reaction temperature may vary within a fairly broad range. such as from about normal room temperature to about 170 0.," although it should not be so low as to cause the reaction to proceed at an inconveniently slow rate, nor so high as to decompose the reactants Y or the product. A satisfactory, though not necessarlly limiting. temperature range is from about 80 to about 150 C. It is convenient to carry out the reaction at the reflux temperature of the solvent employed thereb eliminating the necessity for close temperature control, and thus, the use of a solvent boiling within the aforementioned temperature range is preferred. The ratio of reactants is not critical although a stoichiometric amount or an excess of the salt reactant is preferred to insure a maximum utilization of the bromo compound and conversion thereof to l-acyloxy-chlordene. The amount of 'solvent utilized is also not critical, although a sufllciency thereof to dissolve the reactants and the product is preferred. Large excesses of solvent should be avoided because of the dilution efiect on the rate of the reaction. The solvent may be removed from the reaction product by distillation, at reduced pressures if necessary, and th residue. com ri ing the acyloxy derivative of chlordene, can be purified to obtain pure '1- acyloxy-chlordene. Purification may be accomplished by distillation in vacuo, by crystallization from suitable solvents, by preferential adsorption on porous materials, or by any other means known to the art.

The l-acyloxy-chlordene, thus obtained, has a structural formula and chemical name as previously represented. The nature of R. in said structure is, of course, determined by the acid portion of the salt reactant utilized, Thus, where a a salt of acetic acid is utilized. R would be a methyl group; where a salt of benzoic acid is utilized, 12" would be a phenyl group; where a salt of propionic acid is utilized, R would be an ethyl group; it is thus seen that It represents the acid portion of the salt reactant utilized less the carboxyl group of the acid. 'As previously hexachloroindene. l

. 4 stated, the acid utilized may have up to about twenty carbon atoms, and thus, "R" will be an organic radical containing less than twenty carbon atoms. In the case where a formate salt reactant is utilized, 3" will be a hydrogen atom. Where "R" is a, methylgroup, the compound of the present invention would be named 1-acetoxy-' 4.7-methano 3a.4.7,7a tetrahydro 4,5,65,13,8- In a similar manner. depending on the nature of R." the name of the specific compound can be formulated in accordance with the rules of nomenclature.

The following is a speciflc example of the method of our invention for the purpose of illustration:

Preparation of 1-bromo-chlordene chloride was introduced with a slow rate of stirring. The addition of the bromine solution was carried out at such rate as to maintain the temperature of the reaction vessel at 55 C. After addition was completed, the solution was refluxed for one-half hour to insure complete reaction. The reaction mixture .was then washed with an excess of sodium bisulfite solution, washed with water, and dried in succession with calcium ch10- ride and anhydrous magnesium sulfate. 'The solvent was removed in vacuo and the residue distilled at 0.05 mm. pressure. The product thus obtained boiled at -132 C.

Analysis: Carbon, 27.64%; Hydrogen, 1.36%; Halogen (as chlorine). 59.75%.

Calculated for CloHsClsBlZ Carbon, 28.74%: Hydrogen, 1.21; Halogen (as chlorine), 59.40%.

The product is. therefore, l-bromo-chiordene.

Preparation of I-acetoxy-chlordcne A mixture of 60 grams l-bromo-chlordene was refluxed with 35.4 grams anhydrous sodium acetate in 180 ml. glacial acetic acid for six hours. The solvent was distilled over to yield ml. of the glacial acetic acid used, The residue, comprising l-acetoxy-chlordene was dissolved in benzene (200 ml.) and the extract was filtered. The solvent was then removed from the filtrate at reduced pressure and the l-acetoxy-chlordene as purified by recrystallization from a. benzenepetroleum ether mixture.

The compounds of this invention are useful as insecticides or intermediates in the preparation of insecticides, fungicides, and the like. Thus, the acyloxy group of the compounds of this invention may be replaced with a halogen atom to result in a very potent insecticide. Further, the compounds of this invention may be modified by the introduction of various functional groups into the acyloxy portion thereof either prior to, or after, said acyloxy group has been attached to the chlordene molecule in the 1 position thereof as aforesaid to result in new and valuable compositions having toxic properties.

We claim as our invention:

1. As a new composition of matter, l-acyloxy- 4,7 methano 3a,4,'7,7a tetrahydro 4,5,63,83- hexachloroindene wherein said acyloxy group contains less than 21 carbon atoms.

a,sas,ess

2. A new composition 0! matter eomprisina 1- acetoxy-4,7- methano 3a.4,7.7a-tetrahydro-4.5,- 6,7,8,8-hexachloroindene.

3. The method which comprises reacting 4,7- methano-3a,4,7,7a tetrahydro 4.5,6,7,8,8-hexachloroindene with bromine in the presence of a relatively inert solvent and anlorganic peroxide to iorm 1-bromo-4,'I-methano 3a,4,7.7a-tetrahydro-4,5,6,7,8,8-hexachloroindene, and esterifying said bromo compound to produce l-acyloxy- 4,7 methano 3a,4,7,7a tetrahydro 4,5,63,85- hexachloroindene.

4. The method which comprises reacting the Diels-Alder adduct 01 hexachlorocyclopentadiene and cyclopentadiene with bromine in the presence of a relatively inert solvent and an organic peroxide to form 1-bromo-$,7emethano-3a,4.7,'latetrahydro-4,5,6,'7,8,8-hexachloroindene, and reacting said bromo compound with the metal salt of an organic. carboxylic acid containing less than 21 carbon atoms to produce 1-acyloxy-4flmethano-3a,4,7,7a tetrahydro- 4,5,6,7,8,8-hexachloroindene.

5. The method which comprises reacting 4,7- methano-ilaAflfla tetrahydro 4,5,6,'l,B.8-hexachloroindene with bromine inithe presence of a peroxide and a relatively inert solvent to form i-bromo 4,7-methano-3a,Q.'I, IaQtetrahydro-4,5,- 6,7,8,8-hexach1oroindene, and '-'e'steriiying said bromo compound reacting it with the metal c 6 salt of an organic carboniic acid containing less than 21 carbon atoms in the presence or a relatively inert. solvent to produce i-acyloxy- 4,! methano 3a,4.7,7a tetrahydro 4.5.6.733- hexachloroindene.

6. The method which comprises esterii'ying 1- bromo-lfl methano 3a.4.7.'la-tetrahydro-4.5,- 6.7.8.8-hexachloroindene by reacting it with the metal salt of an organic carboxylic acid containing less than 21 carbon atoms in the presence of a relatively inert solvent to produce i-acyloxy- 4,7 methane 3a,4,'l,7a tetrahydro 4,5,15,73,8- hexachloroindene.

7. A new composition of matter comprising ii'ormwloxy-UI methano 3a,4.'l,7a tetrahydro- 4,5..-I.8.8-hexachloroindene.

8. A new composition of matter comprising 1- beazoyloxy-4.'l-methano 3a,4,l.7a tetra-hydro- 4.5.l,!.8,8-hexachloroindene.

9. A new composition of matter comprising 1- acryloyloxy-efl-methano 3a.4,'l,7a tetrahydro- 4.5.6.7.83-hexachloroindene.

10. A new composition of matter comprising 1- smon n. mom P. owns.

No reterenca cited. I

Certificate of Correction Patent No. 2,528,655 November "Z, 1950 SIMON H. HERZFELD ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 49, for l518 C. read 15180 0.;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 20th day of February, A. D. 1951.

THOMAS F. MURPHY,

Assistant Oommz'ssz'oner of Patents. 

1. AS A NEW COMPOSITION OF MATTER, 1-ACYLOXY4,7 - METHANO -3A,4,7,7A-TETRAHYDRO - 4,5,6,7,8,8HEXACHLOROINDENE WHEREIN SAID ACYLOXY GROUP CONTAINS LESS THAN 21 CARBON ATOMS.
 3. THE METHOD WHICH COMPRISES REACTING 4,7METHANO-3A,4,7,7A - TETRAHYDRO -4,5,6,7,8,8-HEXACHLOROINDENE WITH BROMINE IN THE PRESENCE OF A RELATIVELY INERT SOLVENT AND AN ORGANIC PEROXIDE TO FORM 1-BROMO-4,7-METHANO-3A-TETRAHYDRO-4,5,6,7,8,8-HEXACHLOROINDENE, AND ESTERIFYING SAID BROMO COMPOUND TO PRODUCE 1-ACYLOXY4.7 - METHANO - 3A,4,7,7A - TETRAHYDRO-4,5,6,7,8,8HEXACHLOROINDENE. 